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The electronic landscape of the P-cluster of nitrogenase

Li, Zhendong and Guo, Sheng and Sun, Qiming and Chan, Garnet Kin-Lic (2018) The electronic landscape of the P-cluster of nitrogenase. . (Submitted)

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The electronic structure of the metal cofactors of nitrogenase is central to biological nitrogen fixation. However, the P-cluster and iron molybdenum cofactor, each containing eight metal ions, have long resisted detailed characterization of their low-lying electronic states. Through exhaustive many-electron wavefunction simulation, we report on the full low-energy landscape of the P-cluster in three biologically relevant oxidation states. We trace the origin of the low-lying spectrum to the underlying local atomic states and their global recoupling, and how the interplay between antiferromagnetism, delocalization, and spin frustration as the geometry changes upon oxidation gives rise to the structure of the electronic landscape. Our results support the narrative that many-electron wavefunction simulations stand to provide a resolution of the complicated cofactors in nitrogenase at the electronic level.

Item Type:Report or Paper (Discussion Paper)
Related URLs:
URLURL TypeDescription Paper
Li, Zhendong0000-0002-0683-6293
Guo, Sheng0000-0002-1083-1882
Sun, Qiming0000-0003-0528-6186
Chan, Garnet Kin-Lic0000-0001-8009-6038
Additional Information:Author contributions: Z.L. and G.K.C. designed the study and wrote the manuscript. Z.L. performed the calculations. S.G. contributed to interfacing SP-MPS to SA-MPS used in the BLOCK code. Q.S. contributed to interfacing the PYSCF code with COSMO. All authors contributed to the discussion of the results.
Record Number:CaltechAUTHORS:20181203-110439947
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:91401
Deposited By: Tony Diaz
Deposited On:03 Dec 2018 19:30
Last Modified:03 Dec 2018 19:30

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